CN112279784B - Preparation process of caprylyl hydroximic acid - Google Patents

Preparation process of caprylyl hydroximic acid Download PDF

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CN112279784B
CN112279784B CN202011147312.7A CN202011147312A CN112279784B CN 112279784 B CN112279784 B CN 112279784B CN 202011147312 A CN202011147312 A CN 202011147312A CN 112279784 B CN112279784 B CN 112279784B
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CN112279784A (en
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蔡建
陈晓辉
薛天辉
秦莉锦
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Yantai Oriental Chemical Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
    • C07C259/04—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids
    • C07C259/06—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids having carbon atoms of hydroxamic groups bound to hydrogen atoms or to acyclic carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds

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Abstract

The application relates to the field of chemical synthesis, and particularly discloses a preparation process of caprylyl hydroximic acid, which comprises the following preparation steps: preparing ethyl n-caprylate and caprylyl hydroxamic acid; wherein the preparation steps of the ethyl n-caprylate are as follows: mixing 1-1.5kg of n-octanoic acid and 0.35-0.7kg of ethanol, adding solid super acid, heating and refluxing for 5-7h, filtering to obtain precipitate and filtrate, and distilling the filtrate under reduced pressure to obtain n-octanoic acid ethyl ester; and washing and roasting the obtained precipitate to obtain solid superacid, and recycling the solid superacid to the preparation step of the ethyl n-caprylate for use. The application improves the environmental friendliness of the esterification reaction in the preparation process of the n-octanoyl hydroximic acid by using the solid super acidic catalyst.

Description

Preparation process of caprylyl hydroximic acid
Technical Field
The application relates to the field of chemical synthesis, in particular to a preparation process of caprylyl hydroximic acid.
Background
The octanoyl hydroximic acid is an organic acid which can keep a non-ionized state from acidity to neutrality, has a high-efficiency chelating effect, can inhibit active elements required by mold and limit the environment required by the growth of microorganisms, is an ideal bacteriostatic agent, and is widely applied to the fields of cosmetics, medicines, fine chemicals and the like.
In the preparation process of caprylhydroxamic acid, ethyl caprylate is generally generated by the reaction of caprylic acid and ethanol under the catalysis of sulfuric acid; then, the ethyl caprylate and the hydroxylamine are subjected to hydroximization reaction under the action of a catalyst to prepare the n-caprylyl hydroximic acid.
In related industrial production, the esterification reaction of n-octanoic acid and ethanol generally adopts a homogeneous catalyst, which has the disadvantages of low cost, strong acidity, high catalytic efficiency, easy equipment corrosion, difficult separation of the catalyst and a reaction system, environmental pollution caused by the discharge of a large amount of waste liquid and the like. The development of environmentally friendly solid acid catalysts to replace liquid acids has been an urgent research direction.
Disclosure of Invention
In order to improve the environmental friendliness of the esterification reaction in the preparation process of n-octanoyl hydroximic acid, the application provides a preparation process of octanoyl hydroximic acid.
The preparation process of the octanoyl hydroximic acid adopts the following technical scheme:
a preparation process of caprylyl hydroximic acid comprises the following preparation steps: preparing ethyl n-caprylate and caprylyl hydroxamic acid; wherein the preparation steps of the ethyl n-caprylate are as follows:
mixing 1-1.5kg of n-octanoic acid and 0.35-0.7kg of ethanol, adding solid superacid, heating and refluxing for 5-7h, filtering to obtain precipitate and filtrate, and distilling the filtrate under reduced pressure to obtain ethyl n-octanoate;
and washing and roasting the obtained precipitate to obtain solid super acid, and recycling the solid super acid to the preparation step of the ethyl n-caprylate for use.
By adopting the technical scheme, the sulfuric acid is dissolved in the water and cannot be recycled, so that more waste water is generated; the solid super acid is used as a catalyst, sulfuric acid is replaced, the use of sulfuric acid can be reduced, the solid super acid can be separated from mixed liquid of a reactor through filtration when the reaction is finished, and then the solid super acid is repeatedly used after being washed and roasted, and the catalyst is recycled, so that the cost can be saved, and therefore, the discharge of waste water is reduced in the overall preparation process of the caprylyl hydroximic acid, and the method is environment-friendly.
Preferably, the solid super acid is TiO 2 /ZrO 2 。
By adopting the technical scheme, the method comprises the following stepsBy using TiO 2 /ZrO 2 The reaction of n-octanoic acid with ethanol to produce ethyl n-octanoate can be preferably carried out.
Preferably, the addition amount of the solid super acid is 0.006-0.007kg.
By adopting the technical scheme, when the addition amount of the solid super acid is in the range, the reaction speed is proper.
Preferably, the precipitate is washed by ethanol, the roasting temperature is 500-550 ℃, and the roasting time is 2-3h.
By adopting the technical scheme, the small molecules on the surface of the precipitate can be cleaned by washing with ethanol, and then the small molecules adsorbed in the solid super acid can be removed by roasting, so that the contact area between the solid super acid and a reactant is increased, and the reduction of the catalytic efficiency in the cyclic use is avoided.
Preferably, the preparation method of the solid super acid comprises the following steps:
1) Under the protection of nitrogen, adding 0.9-1.2kg of pretreated styrene and 0.4-0.6kg of polyvinylpyrrolidone into 9-12kg of water, stirring and heating to 75-80 ℃, then adding 0.014-0.018kg of potassium persulfate, stirring and reacting for 7-8h, centrifuging at the rotating speed of 4500-5000r/min for 3-5min to obtain a solid A, and then drying to obtain polystyrene spheres;
2) Putting polystyrene spheres in 13-17kg of distilled water, adding 1.2-1.5kg of zirconium oxychloride and 0.10-0.14kg of titanium sulfate, stirring for 0.5-1h, then dropwise adding ammonia water while stirring to make the pH value reach 10-11, stopping dropwise adding, aging for 22-26h, filtering to obtain a solid B, washing the solid B with water for 3 times, and drying for 5-7h at 100-110 ℃ to obtain a solid C;
3) And (4) placing the solid C in a muffle furnace, and roasting to obtain the solid super acid.
By adopting the technical scheme, under the protection of nitrogen, the polystyrene ball is firstly synthesized, and then the polystyrene ball is used as a template to attach TiO on the surface of the polystyrene ball 2 /ZrO 2 Layer, core-shell structure, then removing polystyrene balls by roasting to produce TiO 2 /ZrO 2 Hollow ball ofPreparation of TiO by grafting 2 /ZrO 2 Particle phase ratio, tiO 2 /ZrO 2 The hollow sphere has larger specific surface area, so that the contact area between the hollow sphere and the reactant is larger, and the catalytic performance is better.
Preferably, the drying temperature in the step 1) is 70-80 ℃, and the drying time is 4-6h.
By adopting the technical scheme, the drying effect is better under the drying condition.
Preferably, in the step 2), the polystyrene spheres are added into distilled water, then ultrasonic dispersion is carried out for 10-20min, and then zirconium oxychloride and titanium sulfate are added.
By adopting the technical scheme, ultrasonic dispersion is beneficial to the rapid dispersion of the polystyrene spheres.
Preferably, the roasting temperature in the step 3) is 500-600 ℃, and the roasting time is 2-3h.
By adopting the technical scheme, under the roasting condition, the solid super acid can generate more acid centers.
Preferably, the preparation steps of the octanoyl hydroximic acid are as follows:
adding 0.003-0.005kg of sodium acetate and 0.001-0.003kg of sodium carbonate into distilled water, stirring until the sodium acetate and the sodium carbonate are dissolved, then adding ethanol with the same volume, stirring for 15-25min, then adding 0.26-0.51kg of hydroxylamine and ethyl n-caprylate, stirring for reaction at 25-30 ℃ for 2-3h, filtering to obtain filtrate, distilling the filtrate under reduced pressure to remove the ethanol, then adding distilled water with the same volume, then dropwise adding 2mol/L of sulfuric acid at the dropwise adding speed of 0.5mL/min until the pH of the solution reaches 2-3, simultaneously precipitating white solids, standing for 1-2h, filtering, washing and drying to obtain the octanoyl hydroxamic acid.
By adopting the technical scheme, the target product with higher purity and yield can be prepared by controlling various conditions of the reaction.
Preferably, in the preparation step, after the equal volume of distilled water is added, the temperature of the mixed solution is reduced to 0-2 ℃, and then the sulfuric acid is dropwise added.
By adopting the technical scheme, the solubility of the product is lower at low temperature, and more products can be separated out.
In summary, the present application has the following beneficial effects:
1. because the solid super acid is adopted, the catalyst is recycled, and the discharge of acidic waste liquid in the esterification reaction step is reduced.
2. In the application, the polystyrene spheres are preferably used as templates, and then the polystyrene spheres are removed by roasting, so that the specific surface area of the solid superacid is larger, and the catalytic effect of the solid superacid is better.
Detailed Description
The present application will be described in further detail with reference to examples.
Examples of preparation of raw materials and/or intermediates
Styrene pretreatment: adding styrene into a 2mol/L sodium hydroxide solution, stirring for 30min, standing, taking supernatant, and washing the supernatant with distilled water until the washed distilled water is neutral; then, anhydrous magnesium sulfate is added, and after drying for 12 hours, filtration is carried out, thus obtaining the pretreated styrene.
Preparation example 1
TiO of preparation example 1 2 /ZrO 2 The raw materials and the use amounts of the solid super acid are shown in table 1, and the preparation steps are as follows:
1) Under the protection of nitrogen, adding pretreated 0.9 styrene and 0.4kg polyvinylpyrrolidone into 9kg of distilled water, stirring and heating to 75 ℃, then adding 0.014kg potassium persulfate, stirring and reacting for 8 hours, centrifuging at the rotating speed of 4500r/min for 5 minutes to obtain a solid A, and then drying the solid A at 70 ℃ for 6 hours to obtain polystyrene spheres;
2) Placing polystyrene spheres in 13kg of distilled water, performing ultrasonic dispersion for 10min, then adding 1.2kg of zirconium oxychloride and 0.10kg of titanium sulfate, stirring for 0.5h, then dropwise adding ammonia water during stirring to enable the pH to reach 10, stopping dropwise adding, then aging for 22h, filtering to obtain a solid B, washing the solid B with water for 3 times, and then drying for 7h at 100 ℃ to obtain a solid C;
3) And (3) placing the solid C in a muffle furnace, setting the temperature at 500 ℃, and roasting for 3h to obtain the solid super acid.
Preparation example 2
TiO of preparation example 2 2 /ZrO 2 The raw materials and the use amounts of the solid super acid are shown in table 1, and the preparation steps are as follows:
1) Under the protection of nitrogen, adding pretreated 1kg of styrene and 0.5kg of polyvinylpyrrolidone into 10kg of distilled water, stirring and heating to 78 ℃, then adding 0.017kg of potassium persulfate, stirring and reacting for 7 hours, centrifuging for 4 minutes at the rotating speed of 5000r/min to obtain a solid A, and then drying for 5 hours at the temperature of 75 ℃ to obtain a polystyrene sphere;
2) Placing polystyrene spheres in 15kg of distilled water, performing ultrasonic dispersion for 15min, then adding 1.38kg of zirconium oxychloride and 0.12kg of titanium sulfate, stirring for 0.5h, then dropwise adding ammonia water while stirring to enable the pH to reach 10, stopping dropwise adding, then aging for 24h, filtering to obtain a solid B, washing the solid B with water for 3 times, and then drying at 105 ℃ for 6h to obtain a solid C;
3) And (3) placing the solid C in a muffle furnace, setting the temperature to be 550 ℃, and roasting for 2h to obtain the solid super acid.
Preparation example 3
TiO of preparation example 3 2 /ZrO 2 The raw materials and the use amounts of the solid super acid are shown in table 1, and the preparation steps are as follows:
1) Under the protection of nitrogen, adding pretreated 1.2kg of styrene and 0.6kg of polyvinylpyrrolidone into 12kg of distilled water, stirring and heating to 80 ℃, then adding 0.018kg of potassium persulfate, stirring and reacting for 6 hours, centrifuging for 3 minutes at the rotating speed of 5500r/min to obtain a solid A, and then drying the solid A for 4 hours at the temperature of 80 ℃ to obtain polystyrene spheres;
2) Placing polystyrene spheres in 17kg of distilled water, performing ultrasonic dispersion for 20min, then adding 1.5kg of zirconium oxychloride and 0.14kg of titanium sulfate, stirring for 1h, then dropwise adding ammonia water in the stirring process until the pH value reaches 11, stopping dropwise adding, aging for 26h, filtering to obtain a solid B, washing the solid B with water for 3 times, and then drying for 5h at 110 ℃ to obtain a solid C;
3) And (3) placing the solid C in a muffle furnace, setting the temperature at 600 ℃, and roasting for 2h to obtain the solid super acid.
Preparation example 4
A solid super acid is prepared by the following steps:
1) Adding zirconium oxychloride and titanium sulfate into distilled water, stirring for 0.5h, then dropwise adding ammonia water while stirring to enable the pH to reach 10, stopping dropwise adding, then aging for 24h, filtering to obtain a solid B, washing the solid B with water for 3 times, and then drying for 5h at 110 ℃ to obtain a solid C;
3) And (3) placing the solid C in a muffle furnace, setting the temperature to be 550 ℃, and roasting for 3h to obtain the solid super acid.
Examples
Example 1
A preparation process of caprylyl hydroximic acid comprises the following steps:
1) Preparation of ethyl n-octanoate:
mixing 1kg of n-octanoic acid and 0.35kg of ethanol, adding 0.005kg of solid superacid, heating and refluxing for 5 hours, filtering to obtain precipitate and filtrate, and distilling the filtrate under reduced pressure to obtain n-octanoic acid ethyl ester;
2) Preparation of octanoyl hydroximic acid:
adding 0.004kg of sodium acetate and 0.002kg of sodium carbonate into distilled water, stirring until the sodium acetate and the sodium carbonate are dissolved, then adding ethanol with the same volume, stirring for 15min, adding 0.26kg of hydroxylamine and ethyl n-caprylate, stirring for reaction for 2h at 25 ℃, filtering to obtain filtrate, distilling the filtrate under reduced pressure to remove the ethanol, then adding distilled water with the same volume, reducing the temperature to 0 ℃, then dropwise adding 2mol/L of sulfuric acid at the dropwise adding speed of 0.5mL/min until the pH of the solution reaches 3, simultaneously precipitating white solid, standing for 1h, filtering, washing with distilled water for 3 times, and then drying for 4h at 70 ℃ to obtain caprylyl hydroximic acid;
wherein, the solid super acid in the step 1) comes from the preparation example 1, and the precipitate obtained in the step 1) is washed with ethanol for 3 times and then roasted at 500 ℃ for 3h to obtain the solid super acid which can be recycled to the step 1) for use.
Example 2
A preparation process of caprylyl hydroximic acid comprises the following steps:
1) Preparation of ethyl n-octanoate:
mixing 1.3kg of n-octanoic acid and 0.5kg of ethanol, adding 0.006kg of solid superacid, heating and refluxing for 6h, filtering to obtain precipitate and filtrate, and distilling the filtrate under reduced pressure to obtain n-octanoic acid ethyl ester;
2) Preparation of octanoyl hydroximic acid:
adding 0.003kg of sodium acetate and 0.003kg of sodium carbonate into distilled water, stirring until the sodium acetate and the sodium carbonate are dissolved, then adding ethanol with the same volume, stirring for 20min, adding 0.40kg of hydroxylamine and ethyl n-caprylate, stirring at 27 ℃ for reaction for 2.5h, filtering to obtain filtrate, distilling the filtrate under reduced pressure to remove the ethanol, then adding distilled water with the same volume, reducing the temperature to 1 ℃, then dropwise adding 2.5mol/L of sulfuric acid at a dropwise adding speed of 0.7mL/min until the pH of the solution reaches 3, simultaneously precipitating a white solid, standing for 1.5h, filtering, washing with distilled water for 3 times, and then drying at 750 ℃ for 3.5h to obtain caprylyl hydroxamic acid;
wherein, the solid super acid in the step 1) comes from the preparation example 1, and the precipitate obtained in the step 1) is washed with ethanol for 3 times, then roasted at 525 ℃ for 2h, and recycled to the step 1) for use.
Example 3
A preparation process of caprylyl hydroximic acid comprises the following steps:
1) Preparation of ethyl n-octanoate:
mixing 1.5kg of n-octanoic acid and 0.7kg of ethanol, adding 0.007kg of solid super acid, heating and refluxing for 7 hours, filtering to obtain precipitate and filtrate, and distilling the filtrate under reduced pressure to obtain n-octanoic acid ethyl ester;
2) Preparation of octanoyl hydroximic acid:
adding 0.005kg of sodium acetate and 0.001kg of sodium carbonate into distilled water, stirring until the sodium acetate and the sodium carbonate are dissolved, then adding ethanol with the same volume, stirring for 25min, adding 0.51kg of hydroxylamine and ethyl n-caprylate, stirring for reaction for 3h at 30 ℃, filtering to obtain filtrate, distilling the filtrate under reduced pressure to remove the ethanol, then adding distilled water with the same volume, reducing the temperature to 2 ℃, then dropwise adding 3.0mol/L of sulfuric acid at the dropwise adding speed of 1.0mL/min until the pH of the solution reaches 2, simultaneously precipitating white solid, standing for 2h, filtering, washing with distilled water for 3 times, and then drying for 3h at 80 ℃ to obtain caprylyl hydroximic acid;
wherein, the solid super acid in the step 1) comes from the preparation example 1, and the precipitate obtained in the step 1) is washed with ethanol for 3 times, and then is recycled to the step 1) for use after being roasted at 550 ℃ for 2 h.
Example 4
A process for preparing octanoyl hydroxamic acid, which is different from example 1 in that the solid super acid in step 1) is obtained from preparation 2.
Example 5
A process for preparing octanoyl hydroxamic acid, which is different from example 1 in that the solid super acid in step 1) is obtained from preparation 3.
Example 6
The preparation process of caprylyl hydroximic acid is different from that in example 1 in that the adopted solid super acid is obtained by cyclic catalysis for 20 times and then roasting.
Example 7
The preparation process of caprylyl hydroximic acid is different from that in example 1 in that the adopted solid super acid is obtained by roasting after 50 times of cyclic catalysis.
Comparative example
Comparative example 1
A process for the preparation of octanoyl hydroxamic acid which differs from example 1 in that the solid superacid was obtained from preparation 4.
Comparative example 2
A preparation process of caprylyl hydroximic acid comprises the following steps:
1) Mixing 14.421g of n-octanoic acid with 5.528g of ethanol, adding 1mL of sulfuric acid, heating and refluxing for 5h, neutralizing with strong sodium oxide solution, and distilling under reduced pressure to obtain a colorless liquid product;
2) Mixing 6.274273g hydroxylamine aqueous solution with 100mL of ethanol, adding 0.3008g of sodium carbonate, adding the colorless liquid product obtained in the step 1) after the sodium acetate and the sodium carbonate are dissolved, then reacting for 2.5 hours at 40 ℃, filtering, removing ethanol by reduced pressure distillation, then adding 100mL of water, reducing the temperature to 0 ℃, then slowly dropwise adding sulfuric acid, adjusting the pH value to 3.5, separating out a white solid, filtering, washing with water, and drying to obtain the octanoyl hydroximic acid.
Performance test
Detection method/test method
The data of the detection of ethyl n-octanoate obtained in examples 1 to 7 and comparative examples 1 to 2 are shown in Table 1.
Purity: its purity was checked by GC (gas chromatography);
wherein, purity = (amount of ethyl n-octanoate/output) × 100%;
yield = (output/charge) × 100%, with charge calculated as the amount of minor reactants charged.
TABLE 1 examination results of ethyl n-octanoate obtained in examples 1 to 7 and comparative examples 1 to 2
Purity (%) Yield (%)
Example 1 99.5 95.3
Example 2 99.4 95.1
Example 3 99.6 95.5
Example 4 99.4 95.2
Example 5 99.5 95.4
Example 6 99.4 95.0
Example 7 99.3 94.8
Comparative example 1 99.1 93.6
Comparative example 2 99.5 94.6
As can be seen from the detection results in Table 1, the purity of the obtained ethyl n-octanoate is above 99.3% and the yield is above 94.8% by using the solid super acid prepared by the method as a catalyst. Compared with the method using sulfuric acid as a catalyst, the method has the advantages that the yield of the ethyl n-octanoate obtained by the method is higher than that of the comparative example 2, namely the sulfuric acid is used as the catalyst, while the purity is high.
As can be seen from the data of example 1 and examples 4-5, the solid superacids obtained in preparation examples 1-3 are clearly different in the morning of catalytic performance.
From the detection data of examples 6-7, it can be seen that the solid super acid still has high catalytic performance after 20 catalytic cycles and 50 catalytic cycles, and the decrease degree in purity and yield is basically negligible, which indicates that the solid super acid of the present application can be recycled for multiple times.
From the data of example 1 and comparative example 1, it can be seen that the purity and yield of the ethyl n-octanoate obtained by using polystyrene spheres as templates and then removing the solid super acid prepared from the polystyrene spheres by calcination are both high.
The data of the detection of the octanohydroxamic acid obtained in examples 1 to 7 and comparative examples 1 to 2 are shown in Table 2.
Purity: the purity of the product is detected by hydrogen nuclear magnetic resonance spectroscopy, wherein,
purity = (amount of octanohydroxamic acid/output) × 100%;
yield = throughput/charge) × 100%, where charge is calculated as the least amount of reactants charged.
TABLE 2 results of examination of octanohydroxamic acid obtained in examples 1 to 7 and comparative examples 1 to 2
Purity (%) Yield (%)
Example 1 95.7 76.2
Example 2 95.6 76.6
Example 3 95.8 76.3
Example 4 95.6 76.3
Example 5 95.7 76.2
Example 6 95.5 76.1
Example 7 95.4 76.2
Comparative example 1 95.7 75.3
Comparative example 2 93.0 75.6
From the test data in table 2, it can be seen that the octanoyl hydroxamic acid obtained by the preparation process of the present application is higher in purity and yield than the octanoyl hydroxamic acid obtained by the comparative example 2, and the catalyst in the n-octanoic acid ethyl ester prepared by the present application does not use sulfuric acid, so that the preparation process is safer, and the industrial wastewater is less.
As can be seen from the data of examples 1-5, the caprylhydroxamic acid prepared herein is higher in both purity and yield than comparative example 2; from the data of examples 6-7, it can be seen that the purity of the obtained octanoyl hydroximic acid is still above 95.4% after the solid super acid is recycled 20 times, even 50 times, and the yield is still higher than that of comparative example 2.
As can be seen from the data of example 1 and comparative example 1, there are clear advantages in purity and yield with the solid super acids prepared in this application.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims (7)

1. A preparation process of caprylyl hydroximic acid is characterized by comprising the following preparation steps: preparing ethyl n-caprylate and caprylyl hydroxamic acid;
wherein the preparation steps of the ethyl n-caprylate are as follows:
mixing 1-1.5kg of n-octanoic acid and 0.35-0.7kg of ethanol, adding solid super acid, heating and refluxing for 5-7h, filtering to obtain precipitate and filtrate, and distilling the filtrate under reduced pressure to obtain n-octanoic acid ethyl ester;
washing and roasting the obtained precipitate to obtain solid super acid, and circulating the solid super acid to the step of preparing the ethyl n-caprylate for use;
the solid super acid is TiO 2 /ZrO 2 (ii) a The preparation method of the solid super acid comprises the following steps:
1) Under the protection of nitrogen, adding 0.9-1.2kg of pretreated styrene and 0.4-0.6kg of polyvinylpyrrolidone into 9-12kg of water, stirring and heating to 75-80 ℃, then adding 0.014-0.018kg of potassium persulfate, stirring and reacting for 7-8h, centrifuging at the rotating speed of 4500-5000r/min for 3-5min to obtain a solid A, and then drying to obtain polystyrene spheres;
2) Putting polystyrene spheres in 13-17kg of distilled water, adding 1.2-1.5kg of zirconium oxychloride and 0.10-0.14kg of titanium sulfate, stirring for 0.5-1h, then dropwise adding ammonia water while stirring to make the pH value reach 10-11, stopping dropwise adding, aging for 22-26h, filtering to obtain a solid B, washing the solid B with water for 3 times, and drying for 5-7h at 100-110 ℃ to obtain a solid C;
3) Placing the solid C in a muffle furnace, and roasting to obtain solid super acid;
in the step 3), the roasting temperature is 500-600 ℃, and the roasting time is 2-3h.
2. The process for preparing octanoyl hydroxamic acid according to claim 1, wherein: the addition amount of the solid super acid is 0.006-0.007kg.
3. The process for preparing octanoyl hydroxamic acid according to claim 1, wherein: washing the precipitate with ethanol, wherein the roasting temperature is 500-550 ℃, and the roasting time is 2-3h.
4. The process for preparing octanoyl hydroxamic acid according to claim 1, wherein: the drying temperature in the step 1) is 70-80 ℃, and the drying time is 4-6h.
5. The process for preparing octanoyl hydroxamic acid according to claim 1, wherein: in the step 2), after the polystyrene spheres are added into distilled water, ultrasonic dispersion is carried out for 10-20min, and then zirconium oxychloride and titanium sulfate are added.
6. The process for preparing octanoyl hydroxamic acid according to claim 1, wherein: the preparation steps of the octanoyl hydroximic acid are as follows:
adding 0.003-0.005kg of sodium acetate and 0.001-0.003kg of sodium carbonate into distilled water, stirring until the sodium acetate and the sodium carbonate are dissolved, then adding ethanol with the same volume, stirring for 15-25min, then adding 0.26-0.51kg of hydroxylamine and ethyl n-caprylate, stirring for reaction at 25-30 ℃ for 2-3h, filtering to obtain filtrate, distilling the filtrate under reduced pressure to remove the ethanol, then adding distilled water with the same volume, then dropwise adding 2mol/L of sulfuric acid at the dropwise adding speed of 0.5mL/min until the pH of the solution reaches 2-3, simultaneously precipitating white solids, standing for 1-2h, filtering, washing and drying to obtain the octanoyl hydroxamic acid.
7. The process for preparing octanoyl hydroxamic acid according to claim 6, wherein: in the preparation step, after the distilled water with the same volume is added, the temperature of the mixed solution is reduced to 0-2 ℃, and then the sulfuric acid is dripped.
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